Process for the manufacture of monobenzoyldiaminoanthraquinones



Patented July 19, 1932 amen STATES IA U L E. moniescnnwsxnon WILMINGTON, n'nnewnnn, gessreuoniro E. r. be four-DE NEMOUES & COMPANY, or WILMINGTON, DELAWARE, VA conronnrron' onnELn- WARE PATEN r oFFrc E; 1

PROCESS FOR- THE MANUFACTURE OF MONOBENZQYLDIAMINOANTHBAQUINONES No Drawing. Application filed June 16,

This invenion relates to a process for the preparation of monobenzoyldiaminoanthraquinones.

Monobenz oyldiaminoanthraquinones are important intermediates in the manufacture of dyestuffs. They can be prepared either by benzoylating nitroaminoanthraquinones and reducing the nitrobenzoylaminoanthraquinones or by partial benzoylation of diaminoanthraquinones.

Processes of the latter art are described in United States Patent #1,660,090 and in British Patent #276,692 (not yet accepted). The former uses benzoic anhydride, the latter benzoyl chloride in connection with agents capable of absorbing acid such as pyridine, quinoline, sodium carbonate, or magnesia.

We have now found that the use of common salt in place of the acid absorbing agents in the benzoyl chloride process has a remarkable efi'ect. It insures a rapid filtration, and if benzoyl chloride be used in proportions of about one molecule to, one molecule of diaminoanthraquinone, the monobenzoyl derivative is the main product.

Excellent results arealso obtained if instead of sodium chloride the chlorides of the alkali and alkaline earth metals are used, as, for instance, potassium chloride, am-' monium chloride, calcium chloride or barium chloride. I p i a l 7 To illustratethe process m'ore fully, the following examples may be given:

Example 1 1925'; Seria1N0. 286,066.

by washing withwater and dried (wt.'about 70 parts). From the filtrate themonobenzoyl derivative crystallizes, when completely cool. It is filtered off and washed with alcohol. It weighs from 210 to. 240

parts. For many purposes its purity willrbe suflicicnt. To obtain it in a chemically pure state itisdi'ssolvedqin10 times its weighto f f Ewa mple fl 20 parts of 1": 4-diaminoanthraquinone and 15 parts of ammoniumchloride are heated with 400 parts of orthodichlorobenzene to r C. and 13.5 parts of benzoyl chloride are run'in :slowly under agitation; During the reaction and a ftercooling 130309 C. the monobenZoyl-l 4-diaminoanthraquinone separates in needles. alcohol then with 5 water, and; dried; It is practically free from the dibenzoylderivative.

a H so In order to secure the monobenzoylcompound in pu'rifiedform', the product of thev centrated sulphuricacid and 2 parts of water added, whereupon the sulphate appears in yellow crystals, which are filtered oil and hydrolyzed by theaddition of water to the violet monobenzoyl-l t-diamin'o anthr equin The proportion given in the examples may,

reaction may be dissolved in ten partsof con v of course, bevaried. If more than one molecule of benzoyl chloride is used, more dibenzoyl compound is formed. ,Using'about 15% less than theory practically no dibenzoyl compound is formed. The temperatures may be raised to the boiling point of'the nitrobenzene or lowered to 150 C. without impairing the result.

I claim:

1. The process of preparing a monobenzoyldiaminoanthraqui'none which comprises j withbenzoyl chloride, the step which comprises reacting the benzoyl chloride and alpha diaminoanthraquinone in substantially molecular proportions in the presence of a;

chloride of a metal of the groupconsisting of alkali metals and alkaline earth metals. I 9. The process ofpreparinga monobenp zoyldiaminoanthraquinone which comprises heating 1:5 diamino'anthraquinone with vbenzoyl chloride above150. 63in the p-r'es-- ence of nitrobenzene and sodium chloride.

1 I In testimony whereof, I aflixmy signature. AU E oMAscnEws i V j,

heating a diaminoa'nthraquinone' with benzoyl chloride in the presence of sodium chlo- V ride. r r

2. The process of preparing a monobenzoyldiaminoanthraquinone which comprises heating a diaminoanthraquinone with benzoyl chloride in the presence of a chloride of a metal of the group consisting of alkali metals'and alkaline earth metals.

3'. The process ofpreparing a monoben-T zoyldiaminoanthraquinone which comprises heatingia diaminoanthraquinone with benzoyl chloride in the presence of a solvent therefor and a chloride of theclass consist ing of sodium chloride, potassium chloride, ammonium chlor1de,'calc1um chloride and barium chloride. e V 4 4.111 the process of preparingmonobenzoyldiaminoanthraquinones which comprises heating a diaminoanthraquinone inthe presence of a solvent thereof with benzoyl chloride, the step which comprises reacting I benzoyl chloride and the diaminoanthraquinof alkali g metals and 5; In the process which. comprises treating analpha diaminoanthraquinone in the presence of a solvent therefor with benzoyl chloride, the step which comprises'reacting benone insubstantially molecular proportions inthelpresence of a chloride ofa metal of 9 the group consistin alkaline earth metals. 2

zoyl chloride and thediaminoanthraquinone. a in substantially molecular proportions in the presence of a chloride of a metal of the group consisting ofalkalimetals and alkaline earth metals. r

v 6. :The process-of preparing a monoben-l Y Z0yld1amlnoanthraquinone which comprlses" heating 1:5 diaminoanthraquinone with.

benzoyl chloride in the presence of nitro benzene and sodium chloride.

7. The process which comprises heating an alpha diaminoanthraquinone'with ben- Y zoyl chloride in the presence of an inert sol- 7 vent of high boilingpoint anda chloride of the class consisting of sodium chloride, po-

7 'tassium chloride, ammonium chloride, cal cl um chlor de and barium chloride.

. 8; In theprocess' which compris'es heating an alpha diaminoanthraquinone in the prescnceof an inert solvent-ofhigh boiling point 

